DE1064524B - Process for the preparation of amine sulfene halides - Google Patents

Description

GERMAN

F16705IVb / 12q

REGISTRATION DATE JANUARY 29, 1955

NOTICE THE REGISTRATION AND ISSUE OF THE EDITORIAL

3 SEPTEMBER 1959

The subject of the patent 965 968 is a method for Production of ammsulfen halides, which then consists Amine disulfides of the general formula

R N —S — S —N

in which R ₁ and R _{2 are} alkyl radicals having 1 to 10 carbon atoms, cycloalkyl radicals or optionally substituted aralkyl radicals, the corresponding ammsulfen halides can be converted with the aid of halogenating agents

Halogemerende means that are used to carry out the The present process are both free halogen, ζ B chlorine or bromine, and halogen-supplying ones Compounds such as ζ B sulfuryl chloride, phosphorus pentachloride, Chlorosulfur and the corresponding bromine and iodine compounds

Preferably when using free halogen If you work in a temperature range between -15 and + 20 ° C, it is advisable to use higher temperatures of halogen-supplying compounds to be used up to about 100 ° C

The inventive method is expediently in an inert diluent, ζ Β carbon tetrachloride, It is irrelevant with regard to the purity of the end products whether the halogen or the halogen-releasing compound in the submitted Solution or suspension of the ammonium disulfide introduced or whether the amine disulfide in a solution or suspension of the halogen or the halogen-supplying compound is added. The diluent can be used for working up distilled off and that which remains as a residue! Process for the preparation of ammsulfen halides

Addendum to patent 965 968

in which R is an alkylene radical, its carbon chain can be interrupted by the heteroatoms oxygen or sulfur, with a halogen at temperatures from -15 to -t-20 ° C in the absence of water to implement.

The subject of the patent 969813 is em method for Production of ammsulfen halides, which then consists To implement amine disulfides of the above constitution with halogen-supplying compounds

In further processing of the inventive ideas on which the main patent and the I additional patent are based, it has now been found that Ammdisulfide of the general formula Applicant:

Paint factories Bayer Aktiengesellschaft, Leverkusen-Bayerwerk

Dr Helmut Freytag, Cologne,

and Dr. Friedrich Lober, Leverkusen, have been named as inventors

Ammsulfenhalogemd by distillation in vacuo or Crystallization can be purified

The ones made accessible by the new process Ammsulfenhalogenide are due to their great reactivity valuable intermediates for organic syntheses, ζ B for the production of rubber auxiliaries foodstuffs, pharmaceuticals and pesticides, represent

Example i

41.6 g of N, N'-dithio-bis-diethylamine (raw) are dissolved in 300 ecm of carbon tetrachloride. Then dry chlorine is passed in at 0 to 5 ° C with stirring until there is a slight excess of chlorine. The excess of chlorine can ζ B with Then the excess chlorine is removed at 0 to 5 ° C in vacuo or by introducing an inert gas The almost clear solution obtained is mixed with animal charcoal and filtered with the exclusion of moisture. last distilled off at 50 ° C. The vacuum distillation gives 39 g of diethylamine sulfenchlond as an orange liquid (bp ₁₃ 62 to 64 ° C)

Example 2

For the solution of 20.8 g Ν, Ν'-dithio-bis-diethylarmn in 25 ecm carbon tetrachloride is dripped with stirring without external cooling, the solution of 13.5 g of sulfuryl chloride (0.1 mol) m 15 ecm carbon tetrachloride The reaction

909 610/397

takes place slightly exothermically with evolution of SO ₂ , the reaction temperature rising to about 40 ° C. The mixture is heated to a bath temperature of 70 to 80 ° C for about 10 minutes and, after cooling, mixed with animal charcoal Removed vacuum. The residue yields 18 g of diethylamine sulfene chloride of the constitution on distillation

; n — be

C ₂ H ₅

Analysis for C ₈ H ₁₈ NSCl

Calculated . N 7.15, S 16.38, Cl 18.12 ° / ₀ ,

Found N 6.67, S 16.60, Cl 18.10 ° / ₀

Example 6

yields 28.5 g of diisobutylamine sulfene chloride with a boiling point of _{0 45} 61 to 64 ° C

Analysis for C ₈ Hi ₈ NSCl

Calculated N 7.15, S 16.38, Cl 18.12%,

found N 6.59, S 16.80, Cl 18.1%

Example 7

20.2 g of crude N, N'-dithio-bis (tert -octyl-n-propylamine), ίο dissolved in 70 ecm carbon tetrachloride, deliver at the In Example 1, 23 g of red-brown liquid and about 1.5 g of tert-octyl-n-propylamine hydrochloride are described The pre-eminent connection of the constitution

as an orange liquid, b.p. ₁₃ 62 to 64 ° C

Example 3

20.8 g (0.1 mol) Ν, Ν'-dithio-bis-diethylamine, dissolved in ao 150 ecm carbon tetrachloride, are dissolved at 0 to 5 ° C with vigorous stirring to the solution of 5.10 ecm bromine (0.2 Gram atom) in 100 ecm carbon tetrachloride, stirred for another 5 minutes at the same temperature, mixed with charcoal and sucked off. After removal of the solvent in vacuo at about 30 to 40 ° C, it is distilled as a dark red liquid with a bp _{0 (1} 32 to 33 ° C

Analysis for C ₄ H ₁₀ NSBr

Calculated N 7.61, S 17.41, Br 43.41%,

found N 7.02, S 17.95, Br 43.25%

Example 4

tert —C _R H _r

η-C ₃ H ₇ '

; n -sei

Boils between 86 and 88 ° C at 0.1 mm
Analysis for C ₁₁ H ₈₄ NSCl

N 5.89, S 13.48, Cl 14.91%,

Calculated
found

N 5.27, S 14.00, Cl 15.10%
Example 8

32 g of crude N, N'-dithio-bis-dibu1ylamm, dissolved in 200 ecm of carbon tetrachloride, are, as described in Example 1, split with chlorine and, after removal of the solvent, sucked off about 1.5 g of undissolved dibutylamine hydrochloride. 32 g ( 82% of the theons) dark brown sulfenchlond Distillation yields dibutylamine sulfenchlond as an orange-colored liquid with a boiling point of _{0> 4 6} , _{s 0.145} 75 to 76 ° C

45 Example 5

16 g (0.05 mol) of N, N'-dithio-bis-dibutylamm, dissolved m IS ecm carbon tetrachloride, are added dropwise to 10.4 g (0.05 mol) phosphorus pentachloride in 60 ecm carbon tetrachloride without external cooling, with stirring the internal temperature at 30 ° C rises Man halt further 5 minutes at 40 to 50 ° C bath temperature After cooling to room temperature, treated with charcoal and conventional work-up subsequent distillation gives 8 g Dibutylaminsulfenchlond the constitution of (C ₄ H ₉ J ₂ N - S - Cl as an orange-colored liquid with a boiling point of 0.08 61 to 63 ° C

17.5 g N.N'-dithio-bis-jS.iS'-dichlorodiathylamm,
80 ecm of carbon tetrachloride dissolved, yeast in the cleavage and work-up described in Example 1 19 g / T-dichloro-diethylamine sulfene chloride as a yellow-brown liquid

Analysis for C ₄ H ₃ NSCl ₃

Calculated N 6.72, S 15.37, Cl 51.01%,

found .. N 6.52, S 15.55, Cl 50.80%

* "Example 9

32 g of crude N.N'-dithio-bis-cyclohexylethylamine, in 200 ecm of carbon tetrachloride are dissolved with chlorine split in the manner described in Example 1 and worked up 32 g of dark brown crude product result. Distillation gives cyclohexylethylammsulfenchlond the formula

60

32 g of crude Ν, Ν'-dithio-bis-diisobutylanun, dissolved in 200 ecm carbon tetrachloride, are, as described in Example 1, split with chlorine and, after removing the solvent, separated from a small amount of undissolved dnsobutylamine hydrochloride. The slightly cloudy, orange-colored Residue (32 g = 82% of theory) as an orange-colored liquid with a boiling point of _{0) 4} 90 to 92 ° C. The dicyclohexylamine sulphene chloride can be obtained in the same way

Example 10

45.5 g Ν, Ν'-dithio-bis-dibenzylamine, in 250 ecm carbon tetrachloride solved, yeast in the procedure described in Example 1 for cleavage with chlorine and Work-up 46 g of dibenzylaminesulfene chloride of the formula

CH,

N-SCl

Claims (1)

Liquid, as a raw product than orange
has been analyzed Analysis for C ₁₄ H ₁₄ NSCl Calculated . . N 5.31, S 12.16, Cl 13.45 · / " found . .. N 5.21, S 12.55, Cl 14.45 · /, Further development of the process for the preparation of aminesulfenhalides according to patent 965 968 and Patent 969 813, characterized in that amine disulfide of the general formula
¹ \ in which R ₁ and R _{2 are} alkyl radicals with 1 to 10 carbon atoms, cycloalkyl radicals or optionally substituted aralkyl radicals, are reacted with halogenating agents under the conditions of the processes mentioned © 909 610/397 8